SRIGAYATRI EDUCATIONAL INSTITUTIONS

INDIA
THERMODYNAMICS UT-03
1. What is Correct about isothermal expansion of ideal gas ?
1) qrev  qirr 2) Wrev  Wirr 3) Wrev  Wirr  O 4) Wrev  Wirr
2. In a change from state A to State B
1) ∆E depends upon the path adopted by „A” to change into “ B”
2) ∆E depends Only on the initial and final state
3) „ w‟ depends only on the initial and final state
4) „q‟ depends only on the initial and final state
3. An ideal gas expands in volume from 1103 m3 to1102 m3 at 300 k against a constant
pressure 1105 Nm2 . The work done is
1) 900 kJ 2) 270 KJ 3) -900 kJ 4) -900 J
4. 16g of oxygen of gas expands isothermally and reversibly at 300 k from 10dm3 to 1000 dm3.
The work done is (inJ)
1) Zero 2) -2872 J 3) +2875 J 4) Infinite
5. based on the first law of thermodynamics which of the following is correct
1) For an isothermal process, q = + w 2) For an isochoric process, U  q
3) For an adiabatic process, U   w 4) For a cyclic process, q = - w
6.  f U of formation of CH 4 g  at certain temperature is -393 KJmol 1 . The value of  f H is
0

1) Zero 2)   f U 0 3)   f U 0 4) Eqal to  tU 0
7. For the Gaseous reaction involving the complete combustion of isobutane :
1) H  E 2) H  E 3) H  E  0 4) H  E
8. The molar enthalpy of vaporization of C6 H 6 at its boiling point ( 353 K ) is 7.4 K cal / mol.
The molar internal energy change of vaporization is :
1) 6.694 K Cal/ mol 2) 62.47 Kcal/mol 3) 8.106 Kcal /mol 4) 7.4 Kcal /mol
9. The H f of CaCO3 s  , CaO s  and CO2 g  are – 1206.9, -635.1 and – 393.5 KJ/mol respectively
0

Their S 0 values are 92.9, 38.2 and 213.7 j/K respectively at 10000 C and 1 atm. The partial
pressure of CO2 in the reaction CaCO3 s  CaO s   CO2 g  is approximately
1) 1.25 atm 2) 9.75 atm 3) 0.03 atm 4) 0.98 atm
10. An ideal gas with Cv = 3R expands adiabatically into a vacuum thus doubling its volume. The
final temperature is given by
T
1) T2  T1  2 1/3  2) T2  T1 3) T2  2T1 4) T2  1
2
11. The reversible expansion of an ideal gas under adiabatic and isothermal conditions is shown
in the figure which of the following statement is correct

1) T3  T1 2) T1  T2
3) Uisothermal  U adiabatic 4) Wisothermal  Wadiabatic

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12. When the following reaction was carried out in a bomb calorimeter, U is found to be -740.0
3
kJ/mol of NH 2CN s  at 300 k NH 2CN s   O2 g   N 2 g   CO2 g   H 2O  l  Calculate H 300k for
2
the reaction
1) -919.57 KJ 2) +738.75 KJ 3) -824.75 KJ 4) -738.75 kJ
13. For the reaction 2CO g   O2 g   2CO2 ; H  500 kJ Two moles of CO and one mole of O2
are taken in a container of volume 2L. They completely from two, moles of CO2 , the gas
deviate appreciably from ideal behavior. If pressure in vessel change from 35 to 20 atm find
the magnitude of U at 500 k
1) 503 kJ 2 ) 400 KJ 3)480 KJ 4) 320 KJ
14. If heat of dissociation of CHCl2COOH  H 2O is
CHCl2COOH  KOH  CHCl2COOH  H 2O is
1) -13.8 kcal 2) +13Kcal 3) -14.4 Kcal 4) -13 kcal
15. For the reaction : X 2O4l   2 XO2 g 
U = 2.1 Kcal S = 20Cal k 1 at 300 k Hence G is
1) 9.3 Kcal 2) 2.7 Kcal 3) -2.7 Kcal 4) -9.3 Kcal
1 1
16. Standard entropies of X 2 , Y2 and XY3 are 60, 30 and 50JK mol respectively For the
1 3
reaction X 2  Y2 XY3 , H  30 KJ to be at equilibrium, the temperature should be,
2 2
1) 1200 k 2) 1000 k 3)750 k 4) 500 k
17. Calculate H f for chloride ion from the following data
0

1 1
H 2 g   Cl2 g   HCl g  ; H 0f  92.4 kJ
2 2

HCl g   nH 2O  H aq  Claq  ; H 0f  74.8 kJ
H 0f of H aq   0.0 KJ
1) -167.2 KJ 2) -165 .2 KJ 3) -157.2 KJ 4) -147.2 KJ
18. The incorrect expression among the following is :
Vf
1) G system = - T 2) In isothermal process, Wrev = nRT ln
Vi
H  T S
0 0
3) ln k  4) K  eG fRT
0

RT
19. A piston filled with 0.04 mol of an ideal gas expands reversibly from 50.0 mL to 375 mL at a
constant temperature of 37.00 C As it does so, it absorbs 208 J of heat. The value of q and w
for the process will be : ( R = 8.314 J/mol k) ( ln7.5 = 2.01 )
1) q = +208 J, w = -208 J 2) q = -208 J, w =- 208 J
3) q = - 208 J w = +208 J 4) q = +208 J , w = +208J
20. The entropy change involved in the isothermal reversible expansion of 2 mole of an ideal gas
from a volume of 10dm3 to a volume of 100 dm3 at 270 C is
1) 42.3Jmol 1K 1 2) 35.8J mol 1K 1 3) 32.3J mol 1K 1 4) 38.3J mol 1K 1
21. A reaction is spontaneous at low temperature but non – spontaneous at high temperature
Which of the following is true for the reaction
1) H  0, S  0 2) H  0, S  0 3) H  0, S  0 4) H  0, S  0
22. The entropy values  in jk 1 mol 1  of H 2 g   130.6 Cl2 g   223.0 and HCl g   186.7 at 298 k
and 1 atm pressure then entropy change for the reaction H 2 g   Cl2 g   2 HCl g  is
1) +540.3 2) +727.3 3) -166.9 4) +19.8

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23. For a reaction H  2 g kJ mol 1 , S  35 kJ mol 1 at what temperature the reaction will be
spontaneous
1) 828. 70 C 2) 828 .7 k
3) Spontaneous at all temperature 4) Not Possible
24. Molar heat of vaporization a liquid is 6 KJ mole 1 If the entropy change is 16 J mole 1K 1 ,
the boiling point of the liquid is
1) 3750 C 2) 375 K 3) 273 K 4) 1020 C
1
25. Given the following thermochemical equations, Zn  O2  ZnO  84000 Cal
2
1
Hg  O2  HgO  21700Cal . According the heat of reaction for the following reaction
2
Zn  HgO  ZnO  Hg  heat is
1) 105700 Cal 2) 61000 Cal 3) 105000 Cal 4) 62300 Cal
26. Molar heat capacity of water in equilibrium with ice at constant pressure is
1) Zero 2) Infinity    3) 40.45kJ K 1mol 1 4) 75.48k J K 1mol 1
27. Since the enthalpy of elements in their natural state is taken to be zero, the heat of formation
  f H  of compounds
1)Is always negative 2) Is always positive 3) May be negative or Positive 4) is zero
28. Identify the intensive quantities from the following
1) Enthalpy 2) Temperature 3) Volume 4) Refractive Index
3
29. Calculate G 0 for conversion of oxygen to Ozone O2 g   O3 g  at 298 K. If KP for this
2
conversion is 2.47 1029
1) 163 KJ mol 1 2) 273 KJ mol 1
3) 106 KJ mol 1 4) 163 Cal mol 1
30. Consider the same expansion but this time against a constant external pressure of ‘1’ atm
1) 2 liter – atm 2) 101.3 J 3) 8 liter – atm 4) 1 liter – atm
0
31. At 60 C , di nitrogen tetroxide is 50 % dissociated calculate the standard free energy change
at this temperature and at one atmosphere
1) 550 kJmol 1 2) 0kJ mol 1 3) +763.8 kJ mol 1 4) -763.8 kJ mol 1
1
32. H 2 g   O2 g   H 2Ol 
2
BE  H  H   x1 ; BE  O  O   x2 ; BE  O  H   x3
Latent heat of vaporisation of water liquid into water vapour = x4 , then  f H ( heat of
formation of liquid water) is
x x
1) x1  2  x3  x4 2) 2 x3  x1  2  x4
2 2
x2 x2
3) x1   2 x3  x4 4) x1   2 x3  x4
2 2
33. The amount of heat evolved when 500cm of 0.1 M HCl is mixed with 200cm3 of 0.2 M NaoH
3

is
1) 2.292 KJ 2) 1. 292 KJ 3) 0.292 KJ 4) 3.92 KJ
NUMERICALS VALUE QUESTIONS
34. A heated iron block at 1270 C loses 300 J of heat to the surroundings which are at a
temperature of 27 0 This process is 0.05 x K 1 Find the value of x
35.  f H 0 of hypothetical MgCl is 125kJ mol 1 and for MgCl2 is -642 KJ Mol 1 . The enthalpy
of disproportionation of MgCl is – 49 x . Find the value of x

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36. If butane on combustion gives carbon monoxide. Find the number of O2 molecule required
37. The value of log10 K for a reaction A  B is
( Given H r0298k  54.07 Jk mol 1
Sr0298k  10 Jk 1 mol 1and
R  8.314 Jk 1mol 1 , 2.303  8.314  298  5705
38. For the reaction , 2CO  O2  2CO2 ; H  560 KJ . Two moles of CO and one mole of O2 are
taken in a container of volume 1 L. They completely from two moles of CO2 , the gases deviate
appreciably from ideal behaviour. If the pressure in the vessel changes from 70 to 40 atm find
the magnitude of U in kJ 500 k ( 1 L.atm = 0.1 kJ)
39. The Work done by a system is 8 joule, when 40 joule heat is supplied to it, what is the
increase in internal energy of system in Joules
40. What is n for combustion of 1 mole of benzene, when both the reactants and the products
are gases at 298K.

KEYSHEET

1 2 2 2 3 4 4 2 5 2 6 2 7 2 8 1 9 2 10 2
11 1 12 4 13 1 14 4 15 3 16 1 17 1 18 3 19 1 20 4
21 4 22 4 23 4 24 2 25 4 26 2 27 3 28 2 29 1 30 3
31 4 32 3 33 1 34 5 35 8 36 3 37 10 38 563 39 32 40 0.5

SOLUTIONS

1. Wrev  Wirr
2. E is a sate fuction
3. W =  P V2  V1 
V2
4. W  2.303 nRT log
V1
5. U  q  w
for an isothermal process, U  O q  w
For an isochoric process, w = 0, U  q
For an adiabatic process q  0, U  w
For a cyclic process, U  0 q  w,
6. The reaction is
CH 4 g   2O2 g   CO2 g   2 H 2Ol 
ng   n p  nr   1  3  2
As  f H 0   f U 0  ng RT
ng  2
H 0  U 0

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 13
7. C4 H10 g   O  4CO2 g   5H 2O g 
2 2 g 
 13  3
n g   9    1 
 2  2
n g   ve
 f H   f E  ng RT
H  E

8. C6 H 6l  C6 H 6 g 
H  E  n g  RT
7.4  E 1 2 103  353
9. CaCO3 s  CaO s   CO2 g 
Kp  PCO
1
2

 0f H    0f H p    0f H R
  635.1   393.5     1206.9 
 178.3 KJ / mol
 0f S   S p0   S R0
= ( 38.2 + 2.3.7 ) – ( 92.9 )
 0f S  159 j / mol  0.159 kJ / mol
Apply 0G  0 H  TAS 0
= 178.3 – 1273  0.159
= -24 .107 KJ /Mol
Also  0f G  2.303RT log K
24.107  2.303  8.314  103  1273log K p
24.107
log k p   0.98
24.374
Kp = 9.75 atm
10. It id free expansion where T  0
11. T3  T1 is incorrect
In an isothermal process, T constant
T2  T1
Area under P-V graph
WIsothermal  Wadiabatic
Now U Isothermal  0
r 1
In adiabatic TV
1 1  T3V3r 1
r 1
T3  v1 
 
T1  v3 
T3  T1 Hence internal energy decreases
U Isothermal  U adiabatic
12. H  U  ng RT
H  74000  0.5  8.314  300
= - 738755 J
= - 738 .75 KJ

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13. U  H  V P
 500   2   35  20    0.1
= -503 KJ
14. Enthalpy of neutralization of strong acid and strong base is
-13.7 Kcal /mol
H  13.7  0.7
= -13.0 KCal
15. X 2O4l   2 XO2 g 
ng  2  0  2
H  U  ng RT
2
 2.1  2   300
1000
H  3.3 KCal
G  H  T .S
20
= 3.3  300 
1000
G  2.7 KCal
1 3
16. S for the reaction X 2  Y2 XY3
2 2
1 3 
S  50    60   30   255
2 2 
For equilibrium G  0  H  T S
H 30000
T   1200k
S 25
17. Given
1
H 2 g    aq   H aq

 e H 0  0  1
2
1 1
H 2 g   Cl2 g   HCl g  ; H 0  92.4 KJ   ii 
2 2
HCl g   nH 2Ol   H aq   Claq  ; H 0  74.8KJ   iii 
(ii) + (iii) – (i)
1
 Cl2 g    aq   e  Claq  ; H   92.4  74.8 KJ  167.2 KJ
2
Heat of formation for Claq   167.2 KJ
18. G0  H 0  T S 0
RT ln K  H 0  T S 0
H 0  T S 0
ln K  
RT
19. The process is isothermal expansion
Hence, q= - w ( U = 0)
∴q = +208J ∴w = -208J
20. Entropy change for an isothermal reversible process is given by
V 100
S  nR ln 2  2  8.314  2.303log  38.3 J .Mol 1 K 1
V1 10
21. G  H  T S when H  0 and S  0 then G will be negative at low temperature and the
reaction will be spontaneous

Page | 6
22. S 0  2 S HCl
0
  S H0 2  SCl0 2   2  186.7  130.6  223.0 

 19.8JK 1mol 1
23. For spontaneous reaction, H  ve; S  ve but in that reaction S is negative, so reaction is
not possible
24. S  16Jmol 1K 1
H vapour 6 1000
Tb. p    375K
Svapour 16
1
25. Using Hess‟s law Zn  O2  ZnO  8400cal 1
2
1
Hg  O2  HgO  21700 cal  2 
2
Subtract (ii) from (i) Zn  HgO2  ZnO   Hg  62300 cal
∴ Heat of reaction = +62300 cal
dq p
26. C P .m 
dT
For H 2O l  H 2O s 
Temperature does not change if some heat is given to the system hence
Ve
C p .m  
zero
27. Conceptual
28. Conceptual
29. G 0  2.303RT log K p and R  8.313JK 1mol 1
 r G 0  2.303  8.314 JK 1mol 1    298 K   log 2.47 10 29 

 163000Jmol 1
 163KJmol 1
30. We have q = -w = Pex(8) = 8 liter.atm
31. N 2O4 g  2 NO2 g 
If N2O4 is 50% dissociated, the mole fraction of both the substances is given by
1  0.5
xN2O4 
1  0.5
2  0.5
xNO2 
1  0.5
0.5
PN2O4  1 atm
1.5
1
PNO4  1 atm
1.5
P 
2
1.5
   1.33 atm
NO4
KP
1.5  0.5
2
PN2O4
Since
 r G 0   RT ln K p
 r G 0   8.314 JK 1mol 1    333K    2.303   0.1239 
 763.8KJmol 1

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32. H   BE reac tan t   BE  products
1
H 2 g   O2 g   H 2Ol 
2
 1 
H   BE  H  H   BE O O 
 2 
  H vap  2  BE O  H 
 
x2
 x1    x4  2 x3 
2
x2
 x1   x4  2 x3
2
33.
HCl  NaOH  NaCl  H 2O
500  0.01 200  0.2
Initial 0 0
1000 1000
moles
 0.05  0.04
Final moles 0.05  0.04  0.01 0.04 0.04
In neutralization of 1 mole of NaOH by 1 mole of HCl heat evolved = 57.3 KJ
To neutralize 0.04 mole of NaOH by 0.04 mole of HCl heat evolved = 57.3 × 0.04KJ = 2.292 KJ
qsys 300
34.  sys S  
Tsys 273  127
300 3 1
  JK
400 5
qsys 300
 surr S  
Tsurr 273  27
300
  1JK 1
300
total S or universe S   sys S   surr S
3 1
  1   0.25 JK 1
4 4

35. 2MgCl  Mg  MgCl2 H  ?

1
Mg s   Cl2 g   MgCl H1  125KJmol 1
2
Mg s   Cl2 g   MgCl2 H 2  642 KJmol 1
H  H 2  2 H1  642   2  125   392 KJmol 1
49 x  392
x 8
9
36) C4 H10 g   O2 g   4CO g   5H 2Ol 
2

NUMERILCAL QUESTIONS
37. For the equilibrium A→B
G0  H 0  T S 0

Page | 8
 G 0  2.303RT log10 K

2.303RT log10 K  H 0  T S 0

2.303RT log10 K  T S 0  H 0

T S 0  H 0 298  10  54.08  1000

log10 K    10
2.303RT 2.303  8.314  298
38) H  U    PV   U  V P

U  H  V P  560  1 30  0.1
Absolute value = 563KJ
39) q = 40 J; w = -8 J (work done by the system)
E  q  w  40  8  32J
15
40) C6 H 6 g   O  6CO2 g   3H 2O g 
2 2 g 
15 1
n  6  3  1    0.5
2 2

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